Polyazo dyestuffs



Patented Mar. 6, 1951 UNITED STATES PATENT oFFIc-Ej-ff Peter Hindermann, Basel, Switzerland, assignor to J. R. Geigy A. G., Basel, Switzerland No Drawing. Application September 7, 1948, Se-

rial No. 48,157. In Switzerland September 15,

The present invention is concerned with the manufacture of copperable disazo and polyazo dyestuffs yielding dyeings with very good fastness properties on cellulose fibres.

The copperable polyazo dyestuffs are very popular because they'are simple to use, arevery fast to light and have generally good wet-fastne'ss 6 Claims. (01.260-460) properties. Their importance and range of use.

has increased in recent years, in particular since the-successful manufacture of polyazo dyestuffs whoseicoppered dyeings on cellulose have adequate f-astness properties even on repeated soap- The new dyestuffs of the present in- Washing.- vention represent a valuable addition to the group of icopperab1e polyazo dyestuffs with outstanding fastness under wet conditions and to light.

1 According to the present invention I have found that valuable yellow toreddish brown disazo and polyazo dyestuffs are obtained when 1 mole of a tetrazotised diamine of the general Formula I H O C 17H:

wherein R represents a member selected from the group consisting of H, Br, Cl, CH3 and CHsO radicals, is coupledin any desired order, on the one hand with 1 mol of a derivative of a ,6- ketocarboxylic acid selected from the group consisting of -pyrazolones and acetoacetic acid arylides and, on the other hand, with 1 mol of a member selected from the group consisting of 5-pyrazolones, acetoacetic acid arylides and naphthol sulfonic acids coupling in o-position to the hydroxyl group. The new copperable polyazo dyestuf fs can thus only be symmetrical with respect to the coupling components if 2 mols of a derivative of a 8-ketocarboxylic acid capable of coupling are used, whereas they must be unsymmetrical if they contain a naphthol-sulfonic acid coupling in the position adjacent to the hydroxyl group, since this is present only once in the dyestufi molecule.

According to the choice of coupling components yellow, yellowish brown or reddish brown dyestuffs are obtained whose coppered dyeings on cellulose are distinguished by very good fastness, even on repeated soap-washing. In choosing the coupling components the solubility ,inflwater The diamines of general Formula I are-obtained by methods known per so (see, e. g'.,' Bri't. Pat. Spec. 'No. 341,970), e. g., by the oneesided reaction of a 3-nitro-4-acyloxybenzoyl halide with 1:5-diaminobenzoic acid to give a 3-nitro- 4-acyloxybenzoylamino-amino compound and then reducing the latter by usual methods to the diamino compound. Alternatively, 2-nitro-5- 'aminobenzoic acid may be acylated with the benzoyl halides named. and reduced by the usual methods to the diamino compound. Next the acyloxy groups are converted to the corresponding diamines ofFormula I by partial hydrolysis.

Benzoylation can be carried out in water or in aqueous or water-free organic solvents; it is expedient to add acid-binding agents, such as, e. g., sodium acetate, sodium carbonate, magnesium oxide or tertiary bases like pyridine or dirnethylaniline. The oxygen-acyl group often splitsoff during benzoylation or reduction, according to the stability of the acyloxy compound andthe method of working. If desired, the acyl group *may be removed from the intermediate product "by mild hydrolysis before or after reduction or only from the completed dyestuff molecule' Instead of the nitroacyloxybenzoyl chlorides used in Pat. Spec. No. 341,970 the nitro-hydroxybenzoyl chlorides made from thec'orres ponding nitrohydroxybenzoic acids by treatment with thionyl chloride may be used, e. g.," 3- nitro-4-hydroxybenzoyl chloride.

There come into question as the first and/or second coupling components, derivatives of a 5- ketocarboxylic acid capable of coupling, by which is to be understood, primarily acetoacetic acid arylides and 5-pyrazolones which may also contain further substituents usual in these compounds.

of the final product should be -considered; in.-

general, dyestuffs containing only one sulphonic acid group are preferable to those with several.

-"droxynaphthalene-7-sulphonic acid,

' the When pyrazolones are used as coupling components instead of acetoacetic acid anilides in dyestuiTs which are otherwise similarly constructed, the coppered dyeings on cellulose are mostly somewhat faster to light, acid or alkali. A couplingpomponent" which has a' particularly favourable effect" on the drawing power on cellulose fibres is 1-(4'-aminophenyl)-3-methyl-5 pyrazolone.

Examples of naphtholsulphonic acids, coupling in the position adjacent to the hydroxyl group, which may be used as first or second coupling component if desired are: the 134-, l':-5-, 2:4-, 2:6-, and 2:7-naphtholsulphonic acids. As substituted naphtholsulphonic acids, there come into question, above all, aminonaphtholsulphonic acids or their derivatives modified at the nitrogen atom, e. g., 2-amino 5-hydroxynaphthalene-7 sulphonic acid and its N-acetyl or N-benzoyl derivatives, 2-phenylamino-5-hydroxynaphthalene- 'a'minoor '2-benzoylamino-6-hydroxynaphthalstated, parts are by weight and temperatures are in degrees centigrade. The relationship of parts by weight to parts by volume is that of kilograms to litres.

Example 1 28.7 parts of 1-(3-amino-4-hydroxybenzoylamino) -4-aminobenzene-3-carboxylic acid are "dissolved cold in 400 parts of water with 8 parts COOH - is salted out, filtered oil? and dried.- It is a'dark ene-B-Sulphonic acid, l-acetylamino-8-hydroxynaphthalene-l-sulphonic acid, 2-acetylamino-5- hydroxynaphthalene-l-sulphonic acid and, as naphtholsulphonic acids containing azo groups, the m'onoazo dyestufis obtained by acid'coupling of 'amihonaphtholsulphonic acids, particularly of 2 amino 5 hydroxynaphthalene-7-sulphonic acid, for example, 1-(4'-hydroxy-3'-carboxy- "phenyl'azo (1')) 2-amino-5-hydroxynaphthal- 'ene-7-sulphonic acid and 1-(4-nitro-2-carboxyphenyl'azo (1')) 2-amino-5-hydroxynaphthalehe-l-sulphonic acid.

The 'copperable polyazo dyestufis according to invention are yellow to reddish brown powders, according to their chemical constitution, which dissolve in water. They dye fibres of natural or regenerated cellulose from a dyebath containing Glaubers salt in yellow, yellowish brown to reddish brown shades which, when cop- "pered, become fast to washing and to light.

Coppering may be carried out either in the dyebath or in afresh bath with the usual copper "salts, e. g., with copper sulphate or copper acetate,

in a neutral or weakly acid medium.

When desired, copper compounds stable towards alkalis may also be used, such as are obtaihed, e.- g, by reacting copper sulphatewith acetic acid anilidemonosulphonic acid.

brown powder giving a yellowish brown solution in water and a yellow'one in concentrated sulphuric acid. It dyes fibres of natural or regenerated cellulose, after-coppered, in yellowish brown shades with excellent fastness. properties.

Similar'yellowish-brown dyestuffs with equally good fastness properties are obtained if, instead of 37.8 parts of 1-(4-aminophenyl)-3-methyl- 5-pyrazolone there are used 34.8 parts of 1- 'phenyl-3 methyl-5-pyrazolone, 19.6 parts of 3- methyl-5-pyrazolone, 41.? parts of 1-(2-chlo'rophenyl) -3-methyl-5-pyra'zolone, 41.? parts of 1- (4 -'chloropheny1) -3-methyl-5-pyrazolone, or 50.6 parts of 1-phenyl-3-methyl-5-pyrazolone- '3- or -4-sulphonarnide, all the other details being as in the above example.

Example 2 28.? parts of 1-(3-amino-4'-hydroxybenzoylamino) -4-aminobenzene-3-carboxylic acid are tetrazotised as described in Example 1, the excess mineral acid is neutralised with sodium carbonate, and the intermediate product formed by combining with 28.7 parts of z-methoxyaceto- After formation of the intermediate product is complete, it is coupled with 23.4 parts of 4-acetylamino-acetoacetic acid anilide, dissolved in 200 parts of water with 5 parts of sodium carbonate, to give the disazo dyes'tufi. The latter, having the formula GOCHa is salted out, filtered off and dried. It is am then dyestuffs with similar properties are oborange powder, giving a yellow solution in water tained.

and concentrated sulphuric acid and yielding Example 4 after-coppered yellow dyeings on cotton and staple fibre which have very good fastness prop- 5 ert'ies. If, instead of 23.4 parts of 4-acetylaminoacetoacetic acid anilide 17.7 parts of acetoacetic acid anilide or 20.? parts of Z-methoxy-acetoacetic acid anilide are used as second coupling component, then similar yellow dyestuffs with equally good properties are obtained.

28.7 parts of 1-(3-amino-4'-hydroxybenzoylamino)4aminobenzene-Bcarboxylic acid are tetrazotised as described in Example 3, the excess mineral acid is neutralised with sodium carbonate and the tetrazo compound is coupled one-sidedly with 31.5 parts of 2-phenylamino-5-hydroxynaphthalene-'l-sulphonic acid dissolved in 400 parts of water and parts of sodium carbonate.

Examples After the intermediate product is formed it is 28.? parts of 1-(3'aminoAhydroxybenzotYl- 4'ammo'acetoa'cgtm amino) 4-aminobenzene-3carboxylic acid are 5 mm amhqe dlssolved wlth 50 of pq dissolved cold in 400 parts of water with a parts carbmate m Parts Water glve the dlsaz" dyestuif of the formula O-HN S0311 coon.

N=N NH-C 0G0 C 0 OH: H N=N--( JH-CONH@NH1 of caustic s da y 1 pa ts f s d nitrite The dyestuff is salted out, filtered off and dried.

are mixed in and the whole added dropwise, in It is a brownish black powder dissolving in water the cold with stirring, to 40 parts of concentrated and concentrated sulphuric acid to give a red yd or a d a d 0 Pa Of Water. After solution. It gives violet-brown after-coppered the excess mineral acid has been neutralised with dyeings with very good fastness pro erties on sodium bicarbonate, the tetrazo compound is coucotton and staple fibre.

p ed with 18.9 pa ts of 1- n0pheny1) 3- If, instead of 19.2 parts of 4-amino-acetoacetic -5-pyrazolone dissolved in 200 Parts Of acid anilide, there are used as second coupling Water and 20 Parts Of Sodium bicarbonate- An component: 17.7.parts of acetoacetic acid anilide aqu us luti n of 8.1 par s of W or 23.4 parts of 4acetylamino-acetoacetic acid hy o y ap D acid, 0 Parts Of anilide, then similar brown dyestuffs with equally sodium carbonate and 150 parts of pyridine is then good fastness properties are obtained.

allowed to flow into the intermediate product.

After stirring for several hours at room tempera- Example 5 ture the disazo dyestuff formed, of the formula 28.7 parts of 1-(3'-amino-4'hydroxybenzoyl- 00011 CHa(|J-(IJH-N=N-NHGO-C OH OH PL 00 N so H 8 NHCOGH;

is salted out, filtered off and dried. It is a dark amino) 4-aminobenzene-3-carboxylic acid are brown powder which dissolves in water and in tetrazotised in the same way as described in Exconcentrated sulphuric acid to give a reddish ample 3, the excess mineral acid is neutralised brown solution. It gives brown after-coppered with sodium bicarbonate and the tetrazo comdyeings on cotton and staple fibre, having very pound then coupled with 18.9 parts of 1-(4- good fastness to light and to wet conditions. aminophenyl)3-methy1-5-pyrazolone dissolved If instead of 28.1 parts of Z-acetylamino-S- in 200 parts of water and 20 parts of sodium bihydroxy-naphthalene-8-sulphonic acid there are carbonate to give the intermediate product. used in the above example: 35.8 parts of 2-(4'- or When coupling is complete, an aqueous solution 3' aminobenzoylamino) 6 hydroxynaphthaof 22.4 parts of 1hydroxynaphthalene4-sullene-B-sulphonic acid, 39.25 parts of 2-(3-aminophonic acid, 20 parts of sodium carbonate and 4' chlorobenzoylamino) 6 hydroxynaphthaparts of pyridine are allowed to flow in. After lene-8-sulphonic acid, or 34.3 parts of Z-benzoylstirring for several hours, formation of the disazo amino6hydroxynaphthalene8-sulphonic acid, dyestuff of the formula coon OH -C-CHN=N-NH-COQOH on t to I iiS complete. It; isrsaltedout, 'filteredzofianddried.

The new dyestuff is a dark-brown powder giving a dirty olive-brownzsolution in water and a .red one, in concentrated sulphuric acid. Cellulose jfibresare dyed in brown shades which have ex- ,cellentifastness properties after treatment with cQpper salts.

If the 22.4 parts of l-hydroxynaphthalenel- =sulphonic acidimthis example are replaced by 22.4 parts of 2-hydroxynaphthalene-7-sulphonic acidgthen a similar dyestuff with equally good properties is obtained.

Example 6 28.? parts of .1-(3'-amino-4 -hydroxybenzoylamino) -4-aminobenzene-3l-carboxylic acid are tetrazotised as described in Example 3 and the excess mineral acidis neutralised Withsodium carbonate. The tetrazo .compound obtained is :coupled with 37.5 parts of v2-.( l -hydroxy-3'--carboxyphenylamino) E-hydroXynaphthaIene-7esulphonic acid dissolved-in v300 parts-of water containing 20 parts of sodium carbonate. After the intermediate product isiormed it is combined with 20.7 parts of 12-methoxyacetoacetic acid anilide, a further 5 parts of sodium carbonate being added, to give a disazo dyestuff, having the formula COOH NH 30311 OOOH The dyestuff is salted out, filtered oil and dried. It is a' brownish black powder dissolving in water to give a violet-red colour and in concentrated sulphuric acid to give a wine-red colour. It dyes cellulose fibres in violet-brownshades which have 55 very good general fastness properties on aftertreating with copper salts. If the 37.5 parts of 2 (4'-hydroxy-3-carboxy-phenylamino) -5-hydroxynaphthalene-'7-sulphonic acid is replaced as starting component by 35.9 parts of 2-(3'-car boxyphenylamino) '8 hydroxynaphthalene-6- sulphonic acid, then a similar dyestuff with equally good properties is obtained.

CHa-CO Example 7 The intermediate compound obtained by uniting the tetrazo compound from 28.? parts of .1- (3'+amino-4-hydroxy-benzoylamino) 4 -ami- ;:n0-benzene-3-carboxylic acid with 18.9 .parts of :1-l(4'-aminophenyl) -.3.-methyl-5-pyrazolone as described-in Example 5 is coupled with, 28.1 parts of -1-acety1amino-8-hydroxy-naphthalene-4-sulphonic acid in the presence of 20 parts of sodium carbonate'and parts of pyridine. The disazo .dyestuif thus formed of the formula COOH is salted out, filtered off and dried. It is a dark brown powder giving a reddish brown aqueous solution and a brownishred one'in sulphuric acid.

It dyes cellulose fibres-in a brown shade. On after-treatment'with copper salts dyeings with remarkable fastness under ,wet conditions and to light are obtained.

If the28.7 parts of 'l-.(3'-amino-4' -hydroxybenzoylamino) 4 aminobenzene -3- carboxylic acid are replaced ,by3L7'paItS of-1-(3 -amino-4- ,hydroxy-5 -methoxybenzoylamino) -4-aminobenzene-3-carboxylic acidzor by32.15 parts of 1-(3'- 1amino-4+hydroxy 6 chlorobenzoylamino) 4- aminobenzene-.3-carboxylic :acid, then similar dyestuffs with equally good ifastness properties are produced.

Example 8 28.? parts of 1-(3'-amino-4'-hydroxybenzoyl- .amino)-4aminobenzene-3-carboxylic acid are COOH N: SOaH is salted out, filtered off and dried. It is a brownish black powder, giving a brown solution in water and an olive-brown one in concentrated sulphuric acid. On natural or regenerated cellulose fibres Example 9 1.5 parts of the dyestuff of Example 1 are dissolved in 3000 parts of water and 2 parts of sodium carbonate contained in a dyebath. 100 parts of cotton are entered into the bath at IO-50, the temperature raised to 90-95 in the course of 30 minutes;- 30 parts of sodium sulphate V70" for 30 minutes.

are added and dyeing continued for 45 minutes at this temperature. Afterwards the dyed goods are rinsed cold and after-treated in a fresh bath with 2 parts of crystalline copper sulphate in 2000 parts of water and 2 parts of 30% acetic acid at Rinsing and drying are carried out as usual. The cotton is dyed in a yellowish brown shade with excellent fastness properties.

The following table contains a number of further examples ilulustrative of the present invention. The method of manufacture is always the same as that of the foregoing examples. In the first column the diamine is shown, in the second,

15 the first coupling component, and in the third, the

second coupling component.

Shade of the after- Diamme of Formula I First coupling component Second coupling component coppered dyeing on cellulose fibres 1- 1 (3 amino 4' hydroxy benzoylamino) 4 4-amino-acetoacetic acid anilide 4-amino-acetoacctic acid anilide. yellow.

aminobcnzene-3-carboxylic acid. 2.-- 1 (3-ami.no-4- hydroxy- 6-methoxybenzoy1- dn dn D amino) -4-aminobenzened-carboxylic acid. 3 1 (3 amino 4 hydroxy 6 chlorobcnzoyl l- (4' -aminopheny1) -3-methy1-5- l-(4 -aminopheny1) -3-methyl -5- yellowish brow amino)-4-aminobenzene-3-carboxylic acid. pyrazolone. pyrazolone. 4 do do 4-amino-acetoacetic acid anilide Do. 5 1 (3 amino -4' hydroxy 5 bromobenzoyl 4-amino-acetoacetic acid anilide l- (4 -aminopheny1) -3-methy1-5- Do.

amino) -4-aminobenzene-3-carboxylic acid. pyrazolone. 6.-- 1 (3 amino 4 hydroxy benzoylamino) 4 1 -(4-aminopheny1)-3-pheny1-5- 1 (4-aminophenyl) -3-phenyl-5- Do.

' aminobenzene-B-carboxylic acid. pyrazolone. pyrazolonc. 7.-- do dn acetoacetic acid anilide Do. 3 do fin 2-methoxy-acetoacetic acid 'Do.

anilide. 9 in dn 2-methoxy-acetoacetic acid ani- Do.

lide-monosulphonic acid. 10.- do do 1-(4-amino-3-sulphopheny1)-3- D methy1-5-pyrazolone. 11 1 (3 amino -4 -hydroxy- 5- methylbenzoyl 1-(4-aminophenyl)-3-mcthy1-5- l- (3-ch1oropheny1)-3-methyl-5- Do.

amino)-4-aminobenzene-3-carboxylic acid. pyrazolone. pyrazolone. 12 (in rin acetoacetic acid-a-naphthalide--. Do. 13 l -(3'-amino-4-hydroxybenzoy1amino)-4-ami- 1 (4 -aminophenyl) -3 -pheny1-5- 2-amino-5 -h ydroxynaphthaleneb r o w n i s h b o r nobcnzene-ll-carboxylic acid. pyrazolone. 7-sulphon1c acid. d w 14 o do monoazo from: 5-amino-2- violet brown.

hydroxybenzene -1 -carboxylic acid acid 2-amino-5-hydroxynaphthalene-7-sulphonic acid. 15.- do do monoazo from: 5-nitro-2-amino- Do.

benzoic acid acid 2-amino-5- hydroxynaphthalene-7-su1- phonic acid. 16-- do Z-acetyl-amino-6-hydroxynaph- 4-methyl sulphonacetoacetic brown.

tha1ene-8-sulphonic-acid. acid amlide. 17.- do 1-acetyl-amino8hydroxynaph Do.

tha1ene-4-su1phonic acid. 18.- 1-(3-aminc-4-hydroxy-fi'-chlorobenzoylamino)- 1-(4'-amino-phenyl)3-methyl-5- 2-acetylammo-5-hydroxy-naph- Do.

4-aminobenzenc-3-carboxylic acid. pyrazolone. thalene-l-sulphonie acid. 19-- 1 (3-amino-4-hydroxy-6-methoxybenzoyl- 1-(4-methylphenyl) -3-methyl- 2- (4 -am1no -benzoylan.mo) -6- Do.

amino)-4-aminobenzene-3-carboxylic acid. fi-pyrazolone. hgdrpxyraaphthalene-B-sulp omc ael 20 1-(3-amino-4'-hydroxy-benzoylamino)-4-amdo 1-hydrpxy naphthalene-fi-sul- Do.

ino-benzene-3-carboxylic acid. phonic acid. 21.- do 1-(4'-amino-phenyl)-3-methyl- 2-(4-hydroxy-3-carb0xy-pheny1- Do.

E-pyrazolone. am ino)-8-hydroxynaphthalene-fi-sulphonic acid. 22 do An 2-(4-amino-benzoylamino)-8- D0.

hydroxynaphthalene-(i-sul phonic acid. 23.- do 4-chloraceto-acetic acid anihilida 2-benzoylammo-5-hydroxy-naphyellowish bro n,

, thalene-7-su1phonic acid. 24.- do 2-chloraceto-acetic acid anilide do D 25.- do 2-ethoxy-acetoacetic acid anilide. 2-acetylamino-5-hydroxy-naph- D thalene-7-sulphonic acid. 26 1-( 3'- a min o-4'-h y d r o x y-6-methylbenzoylacetoacetic acid anilide l-hydroxynaphthalenei-sul- Do.

amino)-4-aminobenzene-3-carboxylic acid. phonlc acid. 27 do I do l-hydroxynaphtha1ene-5-su1- Do.

phonic acid. 28.- 1-(3'-aminc4-hydroxy-6-m c th y l b e n z o y ldo 2-hydroxy-naphthalene-4-sul- Do.

amino)-4-aminobenzene-3-carboxylic acid. phonlc acid. 29 do dn 2-hydroxy-naphtha1ene-6-su1- Do.

phonic acid. 30.- do do 2-hydroxy-naphthalene-7-sul- Do.

. phonic acid. 31 1-(3'-amino-4-hydroxy-b en zoyla mine) -4- monoazo fro m: 5-amino-2- 4-acetylamino-acetoacetic acid brown.

amino-benzene-3-carboxylic acid. hydroxybeuzcnc 1- carboxylic anilide.

acid acid 2-ammo-5-hydroxynaphthalene-7-sulphonic acid. 32 do do 1-phenyl-3 methyl-S-pyrazolona. Do. 1-(3-amino-4-hydroxy'5-n1ethoxyb enzoyl- 1-(4-aminopheny1)-3-methyl-5- l-acetylamlno-fi-hydroxy-naph- Do.

amino)-4-aminobenzene-3-carboxylic acid. pyrazolone. thalene-7 -su1phomc acid. 34 do 3-methyl-5-pyrazolone Z-acetylamino-fi-hydroxy-naph- Do.

thalene-S-sulphonic acid. 35 1-(3'-amino-4'-hydro xy-benzoylamino)-4- do do Do.

amino-benzene-3-carboxylic acid. 36. do do l-hydroxy-naphthalene 4 s u l Do.

phonic acid.

, 13 14 5. A polyazo dyestufi corresponding to the formula coon a N=N S0311 MO N,

6. A polyezo dyestufi corresponding to the formula,

PETER HINDERMANN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,200,414 Cliffe May 14, 1940 2,228,321 Messmer Jan. 14, 1941 2,283,829 Suckfull et a1 May 19, 1942 

2. A POLYAZO DYESTUFF CORRESPONDING TO THE FORMULA 